CN104646019A

CN104646019A - Photocatalyst LiCu3NbWO9 with visible light response and preparation method thereof

Info

Publication number: CN104646019A
Application number: CN201510088364.4A
Authority: CN
Inventors: 方维双; 苏和平; 李洁
Original assignee: Guilin University of Technology
Current assignee: Guangzhou Boyi Intellectual Property Operation Co ltd; Shandong Xingqiang Chemical Industry Technology Research Institute Co ltd
Priority date: 2015-02-26
Filing date: 2015-02-26
Publication date: 2015-05-27
Anticipated expiration: 2035-02-26
Also published as: CN104646019B

Abstract

The invention discloses a wide-frequency and efficient photocatalyst LiCu3NbWO9 with visible light response and a preparation method thereof. The chemical composition formula of the photocatalyst is LiCu3NbWO9. The invention further discloses a preparation method of the material. The photocatalyst obtained by the preparation method disclosed by the invention has the advantages of wide spectral response range, high photoconversion efficiency, good stability and the like. The photocatalyst has the effects of decomposing harmful chemical substances and organic biomass, and sterilizing under the irradiation of visible light; and in addition, the preparation method is simple, the synthesis temperature is low, the cost is low, and the preparation method is suitable for industrial production and application.

Description

Visible light-responded photocatalyst Li Cu 3nbWO 9and preparation method thereof

Technical field

The present invention relates to a kind of visible light-responded photocatalyst Li Cu ₃nbWO ₉and preparation method thereof, belong to inorganic field of photocatalytic material.

Background technology

Along with socioeconomic development, people more and more pay close attention to for the energy and ecological environment, solve energy shortage and problem of environmental pollution be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.

From phase late 1970s, there has been proposed and to utilize in photochemical catalyst decomposition water and the organic matter such as agricultural chemicals in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after absorbing the photon higher than its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO ₂), titanium dioxide has been utilized to decompose organic matters such as the agricultural chemicals in water and in air and odorants, but the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just activity can be shown, can only at indoor or the local work having uviol lamp, almost can not utilize visible ray, this limits the use of titanium dioxide optical catalyst greatly.

Consider the practicality of photochemical catalyst in decomposing harmful substances, utilize sunshine to be indispensable as light source.Irradiate maximum to sunshine medium wavelength intensity of visible ray near 500nm on earth's surface, wavelength is the energy of the visible region of 400nm ~ 750nm is approximately 43% of sunshine gross energy, so in order to efficient utilization, the R and D of bismuth series photocatalyst have achieved a series of great achievement, and bismuthous compound is as BiVO ₄, Bi ₂moO ₆, Bi ₂mo ₂o ₉, Bi ₂mo ₃o ₁₂and Bi ₂wO ₄be in the news and there is good absorption under visible light.A series of niobium (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.Such as, niobate photocatalyst Pb ₃nb ₄o ₁₃, BiNbO ₄and Bi ₂mNbO ₇(M=Al, Ga, In, Y, rare earth element and Fe) etc. with niobium potassium compound oxide photocatalyst as KNbO ₃, KNb ₃o ₈, K ₄nb ₆o ₁₇and K ₆nb _10.6o ₃₀deng all, there is good photocatalysis performance, but its intrinsic photocatalytic effect is very weak or do not have activity in visible-range.

Although photocatalysis research has carried out the several years, the current exploration to visible light-responded photochemical catalyst is the summary of experience drawn by great many of experiments with exploitation major part, in theory also cannot from the crystal structure of compound, composition, the physicochemical properties such as molecular weight are predicted its photocatalysis performance, therefore at present report to have visible light-responded photochemical catalyst kind still very limited, and it is low to there is light conversion efficiency, synthesis difficulty, poor stability and the problem such as spectral response range is narrow, research and develop that new preparation method is simple and to have the visible light-responded high efficiency photocatalyst of wideband be that this area scientific and technical personnel thirst for solving always but are difficult to the difficult problem that succeeds all the time, which greatly limits extensive use and the development of photochemical catalyst.We are to consisting of LiMg ₃nbWO ₉, LiZn ₃nbWO ₉and LiCu ₃nbWO ₉sample carried out Photocatalytic Performance Study.Found that LiCu ₃nbWO ₉band gap is 2.64eV, has excellent visible light-responded photocatalysis performance; LiMg ₃nbWO ₉and LiZn ₃nbWO ₉for insulator, under ultraviolet irradiation, also do not show activity.

Summary of the invention

The object of this invention is to provide and a kind of there is visible light-responded photocatalyst Li Cu ₃nbWO ₉and preparation method thereof.

The chemical constitution formula with visible light-responded photochemical catalyst that the present invention relates to is: LiCu ₃nbWO ₉.

Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:

(1) by 99.9% analytically pure chemical raw material Li ₂cO ₃, CuO, Nb ₂o ₅and WO ₃starting powder press LiCu ₃nbWO ₉composition weigh batching.

(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.

(3) powder step (2) mixed 1000 ~ 1050 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiCu ₃nbWO ₉powder.

Advantage of the present invention: LiCu ₃nbWO ₉the visible light-responded wide frequency range of photochemical catalyst, the high and good stability of light conversion efficiency, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under visible light illumination; Preparation method is simple in addition, synthesis temperature is low, and cost is low, is applicable to industrial production and application.

Detailed description of the invention

To be specifically described the present invention below:

1, in order to obtain the composite oxides used in the present invention, first use solid-phase synthesis to prepare powder, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.

2, in order to effectively utilize light, the size of the photochemical catalyst in the present invention is preferably in micron level, or even nano particle, and specific area is larger.With oxide powder prepared by solid-phase synthesis, its particle is comparatively large and surface area is less, but can pulverize means by ball mill makes particle diameter diminish.

3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Photocatalyst Li Cu ₃nbWO ₉addition be 1g/L; Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make, and obtains the light that wavelength is greater than 420nm, then irradiate photochemical catalyst by wave filter; Catalysis time is set as 60 minutes.

Embodiment 1:

(3) powder step (2) mixed 1000 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiCu ₃nbWO ₉powder.

Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 97.9% to methyl orange clearance in 60 minutes at wavelength.

Embodiment 2:

(3) powder step (2) mixed 1020 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiCu ₃nbWO ₉powder.

Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 98.9% to methyl orange clearance in 60 minutes at wavelength.

Embodiment 3:

(3) powder step (2) mixed 1050 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiCu ₃nbWO ₉powder.

Prepared photochemical catalyst, be greater than the radiation of visible light of 420nm at wavelength under, 60min reaches 98.6% to methyl orange clearance.

The present invention is never limited to above embodiment.Bound, the interval value of each temperature can realize the present invention, do not enumerate embodiment at this.

The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, active carbon or quartz sand etc., and photochemical catalyst can be carried on matrix surface in the form of a film.

Claims

1. a visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described photochemical catalyst is LiCu ₃nbWO ₉;

Preparation method's concrete steps of described photochemical catalyst are:

(1) by 99.9% analytically pure chemical raw material Li ₂cO ₃, CuO, Nb ₂o ₅and WO ₃starting powder press LiCu ₃nbWO ₉composition weigh batching;

(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;

(3) powder step (2) mixed 1000 ~ 1050 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and makes average diameter of particles lower than 2 μm, namely obtain LiCu ₃nbWO ₉powder.